Vanadia-molybdena catalysts for the oxidation of 2-picoline

A study has been made of the influence of catalyst composition on the gas phase oxidation of 2-picoline over mixed vanadium and molybdenum oxides supported on kieselguhr. It is shown that the formation of partial oxidation products is associated with the existence of a mixed oxide phase. The selectivity for the formation of pyridine-2-aldehyde reaches a maximum when one in six vanadium(V) ions in the V₂O₅ lattice is replaced by a molybdenum(VI) ion. It is suggested that the origin of the selectivity is the formation of isolated (V⁴⁺-O) species.     

Dielectric studies of the effect of water on the relaxation properties of nitroglycerine-nitrocellulose mixtures

Dielectric relaxation and water adsorption data are reported on mixtures of nitrocellulose and nitroglycerine which have been exposed to moisture to varying degrees. It was observed that the characteristics of these systems depend on the level of nitrogen in the base polymer. At 10.9% hydroxyl sites still exist which can effectively interact with the moisture, whereas at 12.9% the free hydroxyls appear to be incorporated into the ordered semi-crystalline regions of the polymer. The addition of water to nitroglycerine-nitrocellulose mixtures has little effect on the dominant beta relaxation other than to narrow the distribution of relaxations. The relaxation process is, in this case, associated with a cooperative relaxation of nitroglycerine moieties. Water has the effect of decreasing the cooperativity of the beta relaxation process.     

Mechanical properties of poly(ether-ether-ketone) for engineering applications

An outline of the characteristics of PEEK and the versatility of its compositional forms (micro and macro composites) are given to illustrate its wide potential for success in engineering applications. Although it is necessary to have particular tabulations of mechanical properties for engineering design, these are seldom available and consequently it is argued that an understanding of stiffness, toughness and strength properties are required to fully exploit available manufacturer's data and thus develop the full potential of PEEK and its composites. Stiffness characteristics are considered in terms of a modulus function which is dependent on time under load and temperature. In its composite forms, whether reinforced with short or continuous fibres, stiffness anistropy can be both considerable and complex, but some empirical ground-rules are apparent. For continuous fibre composites even in the form of complex lay-ups, it is also possible to attempt some stiffness prediction from certain pseudo-elastic constants. Toughness of PEEK and its composites is described in terms of both comparative and intrinsic properties. Instrumented falling weight impact data, particularly as a function of temperature enable some insight into ductile-brittle transitions for the unreinforced material, but crack initiation and crack propagation processes for the various fibre reinforced forms. Intrinsic toughness is described in terms of linear elastic fracture mechanics theory. Strength properties are described for static and dynamic loading configurations. In particular, PEEK and its composites are evaluated for increasing test severities for strength characteristics; stress concentration, loading form and test temperature are considered.     

Hydrogen production by the catalytic steam reforming of methanol part 1: The thermodynamics

The thermodynamic equilibria involved in the catalytic steam reformation of methanol to produce hydrogen have been examined over the ranges of pressure 101–3040 kPa, temperature 400–700K and water to methanol feed ratio 1.5–0.67. Four models have been considered based upon possible reaction products and the equilibrium composition of each model calculated. The presence of methane and carbon reduce the quantity and quality of hydrogen produced. The best condition for hydrogen production occurs at 500K in the model in which carbon (soot) and methane gas are excluded and where pressures are low, and water is in excess in the feed. To achieve these conditions in practice the reactions for methane formation, which is thermodynamically favoured, and the appearance of carbon (soot) must be inhibited.     

INVESTIGATION OF THE USE OF LASER-DOPPLER VELOCIMETRY IN TWO-PHASE BUBBLY FLOWS

Understanding the dynamic phenomena of viability loss of shear sensitive cells and bubble breakage and coalescence within airlift reactors requires knowledge of local, liquid-phase hydrodynamics. The laser-Doppler velocimeter (LDV) is a non-invasive instrument which may be used to obtain this information. Experimental procedures and software were developed to detect and measure Doppler bursts in two-phase flow in a split-cylinder airlift reactor. Off-line analysis of the data indicated a detection rate approximately one order of magnitude greater than that observed using an available commercial frequency tracker. Approximately 400 to 500 observations are needed for the ensemble mean to characterize the local mean velocity to within ±5% for a superficial gas velocity of 10.4 cm/s, the highest superficial gas velocity used in these studies. The limitations, prospects, and signal-processing options for LDV in this application are also discussed     

Liquid crystalline acrylic copolymers for high-solids enamel coatings

Carboxyl functional liquid crystalline (LC) acrylic copolymers were synthesized and were compared with carboxyl functional control copolymers of M?_n about 5000–15,000. Both types were crosslinked with a hexakismethoxymethyl melamine (HMMM) resin at 150°C, a temperature below the clearing points of the LC copolymers. Birefringent phases were visible in the crosslinked films made from LC polymers. FT-IR indicated the presence of unreacted COOH in all crosslinked materials. Unreacted COOH groups in crosslinked LC copolymers appeared only slightly higher than those in crosslinked amorphous copolymers. The potential utility of these LC copolymers as binders for thermosetting coatings was assessed. Variables studied were HMMM content, the length of PHBA grafts, T_g and M?_n of the acrylic copolymer backbone, and functionality. Optimum LC copolymers have low backbone T_g (<O°C) and low functionality (< 7.5 mol %). Cured films of such copolymers have both high hardness (> 35 KHN), high impact resistance (> 80 in. ib), excellent adhesion, and good solvent resistance.     

A generalist herbivore in a specialist mode Metabolic,sequestrative, and defensive consequences

Adults of a generalist herbivore, the lubber grasshopper,Romalea guttata, can be converted to functional specialists by feeding them exclusively on catnip,Nepeta cataria. No obvious adverse effects on adult development resulted from this enforced monophagy. Notwithstanding the fact thatR. guttata has had no coevolutionary relationship with this Eurasian mint, it readily sequesters compounds that are identical to or derived from the terpenoid lactones that are characteristic ofN. cataria. R. guttata appears to both biomagnify minor allelochemicals and to sequester metabolites of theNepeta terpenes in its paired defensive glands. The levels of autogenously produced phenolics are not affected by feeding onN. cataria and the defensive secretions of catnip-fed grasshoppers are more repellent to ants than those of wild-fed acridids. Metabolites of theN. cataria monoterpenes are sequestered in the defensive glands when catnip is added to the natural diet ofR. guttata. The ability of a generalist,R. guttata, to facilely bioaccumulate a potpourri of foreign allelochemicals when feeding in a specialist mode is analyzed in terms of its biochemical, physiological, and functional significance. Sequestration is examined as a response to the enteric effronteries represented by the phytochemicals that can be characteristic of the overload in a monophagous diet.     

Soap-based detergent formulations: X. Nature of detergent deposits

The cumulative deposition of detergent residue on unsoiled cotton and polyester-cotton permanent press finish cloth was determined for a variety of detergent formulations after washing 25 consecutive times in 300 ppm hard water in a laboratory Tergotometer. Included in this study were: a phosphate-built laundry detergent, two carbonate-built detergents, tallow soap and various tallow soap formulations with anionic and amphoteric lime soap dispersing agents, and a glassy sodium silicate. Sample swatches washed with each formulation were analyzed for calcium, magnesium, and organic acid content. Fabric washed with the carbonate detergents showed the highest calcium and magnesium content, while those washed with the phosphate detergent and the soap-lime soap dispersant-builder formulations had the lowest. Fabric washed with soap alone had a much higher fatty acid residue than those washed with the other detergent formulations. However, the amount of organic acids left on the fabric after washing with a soap-lime soap dispersing agent formulation was no greater than that produced by phosphate- and carbonate-built detergents. The presence or absence of deposits also was verified visually with a scanning electron microscope. Each formulation also was tested for detergency by measuring the soil buildup in a multiwash procedure. Generally, the buildup of soil paralleled the deposit of detergent residue on the unsoiled cloths.     

The Thermal Stability of Linear Trans-quinacridone Pigments

Although linear trans-quinacridone was first synthesized some forty years ago, it has appeared as a commercial pigment much more recently and was the first red pigment of a new chemical class for a very long time. It can be prepared with a number of different crystal structures all having the same chemical formula, but different hues. The γ-form is the most stable. The transformations between this form and the β-form, which can be brought about by heat and solvents, have been examined by a combination of differential thermal analysis, scanning electron microscopy and X-ray diffraction.     

Oxidation of SiCf/SiC‐HfB2 Composites under Laser Heating

Ceramic matrix composites with Sylramic^TM and CG Nicalon^TM SiC fibers and SiC‐HfB₂ matrices derived from a combination of polymer‐derived SiC ceramic and HfB₂ particulate slurries were prepared. The composites were tested for oxidation resistance by laser heating at 2 MW/m² to achieve temperatures near 1600°C. The oxidation resistance was compared between uncoated CG Nicalon^TM and BN‐coated Sylramic^TM fiber‐based composites. Oxidation resulted in precipitated nano‐sized HfO₂ independent of the fibers and fiber coatings.